1,2,4-Triazol-3-ol esters

ABSTRACT

Triazolyl phosphoric acid esters of the formula WHEREIN R1 represents a phenyl group substituted by one or more bromine and/or iodine atoms, the same or different lower alkyl, lower alkoxy, lower alkylthio, lower alkyl-SO, lower alkyl-SO2, or O2N groups or substituted by at least one chlorine atom and at least one bromine or iodine atom, a lower alkyl, lower alkoxy, lower alkylthio, lower aklyl-SO, lower alkyl-SO2 or O2N group or R1 represents an unsubstituted or halogenated, alkylated and/or alkoxylated phenyl-lower alkyl or diphenylmethyl group, R2 and R3 each represent lower alkyl and X and Y are each oxygen or sulphur, their manufacture and their use in pest control.

United States Patent n91 Dawes et al.

[ Jan. 28, 1975 l l 1,2,4-TRIAZOL-3-OL ESTERS [73] Assignee: Ciba-Geigy Corporation, Ardsley,

22 Filed: Oct. 16, 1972 21 Appl. No.:298,160

[30] Foreign Application Priority Data Oct. 21, 197l Switzerland 15340/7l Aug. 24, l972 Switzerland 12542/72 [52] U.S. Cl. 260/308 R, 424/200 [51] Int. Cl C07d 55/06 [58] Field of Search 260/308 R [56] References Cited OTHER PUBLlCATlONS Chemical Abstracts, abstracting South African Pat. No. 68/0347] 31 Oct. I968 Chemical Abstracts, Vol. 7] Abstract l0l86lc (1969) Primary ExaminerHenry R. Jiles Assistant ExaminerRobert T. Bond Attorney, Agent, or FirmHarry Falber; Frederick H. Rabin [57] ABSTRACT Triazolyl phosphoric acid esters of the formula N YR;

wherein R represents a phenyl group substituted by one or more bromine and/or iodine atoms. the same or different lower alkyl. lower alkoxy, lower alkylthio, lower alkylSO, lower alkyl-SO or O N groups or substituted by at least one chlorine atom and at least one bromine or iodine atom, a lower alkyl, lowcr alkoxy, lower alkylthio, lower aklyl-SO, lower alkyI-SO or O N group or R, represents an unsubstituted or halogenated, alkylated and/or alkoxylated phenyl-lower alkyl or diphenylmethyl group, R and R each represent lower alkyl and X and Y are each oxygen or sulphur. their manufacture and their use in pest control.

10 Claims, No Drawings 1 1,2,4-TRIAZOL-3-OL ESTERS The present invention relates to new triazolyl phosphoric acid esters, their manufacture and their use in pest control.

According to the present invention there are provided triazolyl phosphoric acid esters corresponding to the formula wherein R represents a phenyl group substituted by one or more bromine and/or iodine atoms, the same or different lower alkyl, lower alkoxy, lower alkylthio, lower alkyl-SO, lower alkyl-S or O N groups or substituted by at least one chlorine atom and at least one bromine or iodine atom, a lower alkyl, lower alkoxy, lower alkylthio, lower alkyl-SO, lower alkyl-SO or O N group or R represents an unsubstituted or halogenated, alkylated and/or alkoxylated phenyl-lower alkyl or diphenylmethyl group, R and R each represent lower alkyl and X and y are each oxygen or sulphur.

By lower alkyl, alkoxy or alkylthio there is to be understood in each case a straight or branched chain group having 1 to 5 carbon atoms, for example methyl, methoxy, methylthio, ethyl, ethoxy, ethylthio, n-propyl, propoxy, isopropyl, n-butyl and n-pentyl, as well as their isomers. By phenyl-lower alkyl groups are to be understood those groups which have one to four, preferably one or two, carbon atoms in the side chain. Examples of such groups are benzyl,

Preferred on account oftheir activity are compounds of formula I wherein R, is 2-mcthyl-4-chlorophenyl, 2-

nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 4- ethoxyphenyl, 4-methylmercapto-phenyl, 4- bromophenyl, benzyl,

Jill s R and R are each methyl, ethyl or n-propyl, X is sulphur and y is oxygen or sulphur.

The compounds of formula I may be manufactured by reacting (a) a hydroxytriazole of the formula with a phosphoric acid halide of the formula YRt (ll!) in the presence of an acid binding agent, or (b) a salt of hydroxytriazole of formula ll with a phosphoric acid halide of formula III.

In formulae II and [II the symbols R, to R and X have the meanings given for formula I and Hal stands for fluorine, chloride, bromine or iodine, especially chlorine or bromine. Suitable salts of hydroxytriazoles of formula II for use in the process according to the invention are for example those of monovalent metals, particularly the alkali metal salts, but others may also be used, for example salts of monovalent heavy metals.

The following bases may be used, for example, as acid binding agents: tertiary amines such as triethylamine, dimethyl aniline, pyridine bases, inorganic bases, such as hydroxides and carbonates of alkali and alkaline earth metals, preferably sodium and potassium carbonate.

The reactions are preferably carried out in a solvent or diluent inert to the reactants. For this, the following are, for example, suitable: aromatic hydrocarbons such as benzene, toluene, petroleum ether, halohydrocarbons, chlorobenzene, polychlorobenzenes, bromobenzene, chlorinated alkanes with l to 3 carbon atoms, ethers such as dioxane, tetrahydrofuran; esters such as ethyl acetate; ketones such as methyl ethyl ketone, diethyl ketone, nitriles, etc.

The starting materials of formula ll are partly known compounds which can be made by methods known per se. These compounds are obtained, for example, by reacting a correspondingly substituted semicarbazide with orthocarboxylic acid ethyl esters, e.g., alkyl formates, or by first formulating a correspondingly substituted semicarbazide followed by ring closure under alkaline conditions.

In this way, the following novel starting materials of formula ll may, for example, be made:

CII (J-01]: Melting point,

The compounds of formula I have broad spectrum biocidal activity and can be used for combating various vegetabie and animal pests, for example as viricides, selective herbicides and molluscicides.

They are effective abova all agai'nst all development stages such as eggs, larvae, nymphs, pupae and adults ofinsects and representatives of the order Acarina such as mites and ticks.

The compounds of formula I can be used for example against the following insects or representative of the order Acarina: Insects of the families: Teltigonidae, Gryllidae, Gryllotalpidae, Blattidae, Peduviidae, Phyrrhocoriae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymatriidae, Pyralidae, Culicidae, Tipulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae as well as Acarina of the families lxodidae, Argasidae, Tetranychidae and Dermanyssidae.

The insecticidal and/or acaricidal action can be substantially broadened and matched to given circumstances by the addition of other insecticides and/r acaricides.

As additives, the following active substances are, for example, suitable:

Organic phosphorus compounds Bis- 0,0-diethylphosphoric acid anhydride (TEPP) (DICHLOR- 4 0,0-diethyl-O(or S)-2-(ethylthio)-ethylthiophosphate (DEMETON) S-ethylthioethyl-QO-dimethyl-dithiophosphate (THIOMETON) 0,0-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE) 0,0-diethyl-S-Z-ethylthio)ethyldithiophosphatc (Dl- SULFOTON) 0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETON METHYL) 0,0-dimethyl-S-( l ,2-dicarbethoxyethyldithiophosphate (MALATHION) 0,0,0,0-tetraethyl-S,S-methylene-bisdithiophosphate (ETHION) O-ethyl-S,S,-dipropyldithiophosphate 0,0-dimethyl-S-(N-methyl-N- formylcarbamoylmethyl)-dithiophosphate (FOR- MOTHION) 0,0-dimethyl-S-(N-methylcarbamoylmethyl)dithiophosphate (DIMETHOATE) 0,0-dimethyl-O-p-nitrophenylthiophosphate (PA- RATHlON-METHYL) 0,0-diethyl-O-p-nitrophenylthiophosphate (PARA- THION) O-ethyl-O-p-nitrophenylphenylthiophosphate (EPN) 0,0-dimethyl-O-(4-nitro-m-tolyl)thiophosphate (FENITROTHION) 0,0-dimethyl-O-2,4-5-trichlorophenylthiophosphate (RONNEL) O-ethyl-O,2,4,5-trichlorophenylethylthiophosphate (TRICHLORONATE) 0,0-dimethyl-O -2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS) 0,0-dimethyl-O-(2,5-dichloro-4-jodphenyl)- thiophosphate (JODOFENPHOS) 4-tert. butyl-2-chl0rophenyl-N-methyl-O- methylamidophosphate (CRUFOMATE) 0,0-dimethyl-O-(3-methyl-4- methylmercaptophenyl)thiophosphate ION) lsopropylamino-O-ethyl-O-(4-methylmercapto-3- methylphenyl)-phosphate (FENTH- 0,0-diethyl-O-p-(methylsulphinyl)phenylthiophosphate (FENSULFOTHION) O-p-(dimethylsulphamido)phenyl-0,0 dimethylthiophosphate (FAMPHUR) 0,0,0',O-tetramethyl-0,0-thiodi-P-phenylenethiophosphate O-ethyl-S-phenyl-ethyldithiophosphate 0,0-dimethyl-O-(a-methylbenzyl-3-hydroxycrotonyl)phosphate Z-chloro-l-(2,4-dichlorophenyl)vinyldiethylphosphate (CHLORFENVINPHOS) l-chloro-l (2,4,5-trichlorophenyl)vinyldimethylphosphate O-[2-chloro-l-(2,5-dichlorophenyl)]vinyl-0,0-

diethylthiophosphate Phenylglyoxylonitriloxim-0,0-diethylthiophosphate (PHOXlM) 0,0-diethyl-O-(3-chIoro-4-methyl-2-oxo-2-H-lbenzopyran-7-yl)-thiophosphatc (COUMAPHOS) 2,3-p-dioxandithiol-S,S-his((),()-dicthyldilhiophosphate) (Dioxathion) 5-[(6-chloro-2-oxo-3-benzoxazolinyl)methyl]0,0-

diethyldithiophosphate (PHOSALONE) Z-(diethoxyphosphinylimino)-l,3-dithiolane 2-chloro-4,5-dimethylphenyl-N-methylcarbamate 2-( l ,3-dioxolan-2-yl)phenyl-N-methylcarbamate (DIOXACARB) 2-(4,5-dimethyl-l,3-dioxolan-2-yl)phenyl-N- methylcarbamate 2-(1,3-dioxolan-2-yl)phenyl-N,N-dimethylcarbamate 2( l ,3-dithiolan-2-yl)-N,N-dimethylcarbamate 2-( l ,3-dithiolan-2-y1)phenyl-N,N-dimethylcarbamate 2-isopropoxyphenyl-N-methylcarbamate (APROCARB) 2-(2-propinyloxy)phenyl-N-methylcarbamate 3-(Z-propinyloxy)phenyl-N-methylcarbamate 2-dimethylaminophenyl-N-methylcarbamate 2-diallylaminophenyl-N-methylcarbamate 4-diallylamino-3,5-xylyl-N-methylcarbamate LYXICARB) 4-benzothienyl-N-methylcarbamate 2,3-dihydro-2-methyl-7-benzofuranyl-N- methylcarbamate 3-methyl-1-phenylpyrazol-5-yl-N,N-dimethylcarbamate 1-isopr0pyl-3-methylpyrazol-5-yl-N,N-dimethylcarbamate (ISOLAN) 2-dimethylamino-5,6-dimethylpyrimidin-4-yl-N,N-

dimethyl-carbamate 3-methyl-4-dimethylaminomethyleneiminophenyl-N- methylcarbamate 3-dimethylamino-methyleneiminophenyl-N- methylcarbamate (FORMETANATE) and their salts l'methylthio-ethylimino-N-methylcarbamate (ME- THOMYL) 2-methylcarbamoyloximino-l ,3v-dithiolane 5-methyl-2-methylcarbamoyloximino-1,3-

oxythiolane 2-( l-methoxy-2-propoxy)phenyl-N- methylcarbamate 2-( l-butin-3-yl-oxy)phenyl-N-methylcarbamate l-dimethylcarbamyl-l-methylthio-O'methylcarbamyl-formoxime 1-(2-cyanoethylthio)-O-methylcarbamylacetaldoxime 1-methylthio-O-carbamyl-acetaldoxime O-(3 sec.butylphenyl)-N-phenylthio-N- methylcarbamate 2,5-dimethyl-1,3-dithioland-2(O-methylcarbamyl)- aldoxime) O-2-diphenyl-N-methylcarbamate 2-(N-methylcarbamyl-oximino)-3-chlorobicyclo[2.2.l]heptane Z-(N-methylcarbamyl-oximino)- bicyclo[2.2.1]heptane 3-isopropylphenyl-N-methyl-N-chloroacetylcarbamate 3-isopropylphenyl-N-methyl-N-methylthiomethylcarbamate O-(2,2-dimethyl-4-chloro-2,3-dihydro-7- benzofuranyl-N-methylcarbamate 0-(2,2,4-trimethyl-2,3-dihydro-7-benzofuranyl)-N- methylcarbamate O-naphthyl-N-methyLN-acetyl-carbamate O-5,6,7,8-tetrahydronaphthyl-N-methyl-carbamate 3-isopropyl-4-methylthio-phenyl-N- methylcarbamate 3,5-dimethyl-4-methoxy-phenyl-N-methylcarbamate 10 3-methoxymethoxy-phenyl-N-methylcarbamate 3-allyloxyphenyl-N-methylcarbamate 2-propargyloxymethoxy-phenyl-N-methyLcarbamate 2-allyloxyphenyl-N'methyhcarbamate 4-methoxycarbonylam ino-3-isopropylphenyl-N- methyl-carbamatc 3,5-dimethyl-4-methoxycarbonylamino-phenyl-N- methyl-carbamate 2-'y -methylthiopropylphenyl-N-mcthyl-carbamate 3-(a-meth0xymethyl-2-propenyl phenyl-N-methylcarbamate 2-chloro-5-tert.-butyl-phenyl-N-methyl-carbamate 4-(methyl-propargylamino)-3,5 -xylyl-N-methylcarbamate 4-(methyl-'y-chloroallylamino)-3,5-xylyl-N-methylcarbamate 4-(methyl-B-chloroallylamino)--3,5-xylyl-N-methylcarbamate l-(/3-ethoxycarbonalethyl)-3-methyl-5-pyrazolyl- N,N-dimethyl-carbamate 3-methyl-4-(dimethylamino-methylmercaptomethyleneimino)phenyl-N-methylcarbamate l,3-bis(carbamoylthio )-2-(N,N-dimethylamino)- propanehydro-chloride 5,5-dimethylhydroresorcinoldimethylcarbamate 2-[ethyl-propargylamino]-phenyl-N- methylcarbamate 2-[methyl-propar-gylamino]-phenyl-N- methylcarbamate Z-[dipropargylamino]-phenyl-N-methylcarbamate 4-[dipropargylamino]-3-tolyl-N-methylcarbamate 4-[dipropargylaminol-3,5-xylyl-N-methylcarbamate 2-[allyl-isopropylamino]-phenyl-N-methylcarbamate 3-[allyl-isopropylamino1-phenyl-N-methylcarbamate Chlorinated Hydrocarbons y-hexachlorocyclohexane [GA.MMEXANE; LIN- DAN; 'y HCH] l,2,4,5,6,7,8,8-octachloro-3a,4,7,7atetrahydro-4,7-

methylenindane [CHLORDAN] l,4,5,6,7,8,8-heptachloro, 3a,4,7,7a-tetrahydro-4,7-

methylenindane [HEPTACHLOR] l,2,3,4,10,10-hexachloro-l,4,4a,5,8,8a-hexahydroendo-l,4-exo-5,8-dimethanonaphthalene [AL- DRIN] I,2,3,4,10,l0-hexachloro-6,7-epoxyl,4,4a,5,6,7,8,8a-oxtahydro-exo-l,4-endo-5,8- dimethanonaphthalene(DIELDRIN) l,2,3,4,10,l0-hexachloro-5,7epoxyl,4,4a,5,6,7,8,8a-octyhydro-endo-endo-5,8- dimethanonaphthalene [ENDRIN] The favourable warmblooded toxicity of the compounds of formula I and of materials containing them is also to be noted.

The active substances of formula I also have fungicidal properties against phytopathogenic fungi on various culture plants such as cereals, maize, rice, vegetables, ornamental plants, fruit trees, vines, field fruits, etc.

Using the new active substances, fungal infections arising on the fruits, blooms, leaves, stems and roots can be inhibited or eliminated, whereby even later growing plant parts remain protected from such infections. The active substances of formula I are effective especially against the following classes: Oomycetes, Zygomycetes, Ascomycetes, Basidiornycetes and Denteromycetes.

Furthermore, the new active substances can be used for the treatment of seeds, fruit, tubers, etc., for protecting them against fungal infection, for example by smut fungi of all types.

For broadening the spectrum of activity, there can be mixed in with the active substances of Formula I, as well as the acaricides and insecticides noted above, for example, also bactericides, fungistatic agents, bacteriostatic agents, nematocides and/or the following fungicides:

dodecylguanidine acetate (DODINE) pentachloronitrobenzene (QUINTOZENE) pentachlorophenol (PCP) 2-(1-methyl-n-propyl)-4,6-dinitrophenyl-2-methylcrotonate (BINAPACRYL) 2-( l-methyl-n-heptyl)-4,6-dinitrophenylcrotonate (DINOCAP) 2,6dichloro-4-nitroaniline (DICHLORAN) 2,3,5,6-tetrachloro-benzoquinone (1,4) (CHLOR- ANIL) 2,3-dichloro-naphthoquinone (1,4) (DICHLONE) N-(trichloromethylthio) phthalimide (FOLPAT) N-(trichloromethylthio) cyclohex-4-en-1,2-

dicarboximide (CAPTAN) N-( l,1,2,2-tetrachloroethylthio)cyclohex-4-en-l,2-

dicarboximide (CAPTAFOL) N-methansulfonal-N-trichloromethylthiochloroaniline N'-dichlorofluoromethylthio-N,N-dimethyl-N- phenylsulfamide (DICHLOFLUANID) O-ethyl-S-benzyl-phenyldithiophosphate 0,0-diethyl-S-benzy-thiolphosphate disodium-ethylene-l ,2-bis-dithiocarbamate (NABAM) zinc-ethylene-l ,Z-bis-dithiocarbamate (ZINEB) manganese-ethylene-l,Z-bis-dithiocarbamate (polymeric) (MANEB) tetramethylthiuramdisulfide (THIRAM) l-oxy-3-acetyl-6-methyl-cycl0hexene-(5)dione-(2,4)

(DEHYDROACETIC ACID) 8-hydroxyquinoline (8-QUINOLINOL) 2-dimethylamino-6-methyl-5-n-butyl-4-hydroxypyrimidine methyl-N-benzimidazole-2-ylN-(butylcarbamoyl)- carbamate (BENOMYL) 2-ethylamino-6-methyl-5n-butyl-4- hydroxypyrimidine 2,3-dicyano-1,4-dithia-anthraquinone NON) 2-(4=thiazolyl)-benzimidazole 3,5-dimethyltetrahydro-1,3,5-thiadiazin-2-thione (DAZOMET) 2,3-dihydro--carboxanilido-6-methyl-1,4-oxathine pentachlorobenzyl alcohol.

Additionally, the new compounds of formula I possess exceptionally good nematocidal properties, and can be used, for example, to combat the following plant parasitic nematodes: Meloidogyne sp., Heterodera sp., Ditylenchus sp., Pratylenchus sp., Paratylenchus sp., Anguina sp., Helicotylenchus sp., Tylenchorhynchus sp., Rotylenchulus sp., Tylenchulus semipenetrans, Radopholus similus, Belonolaimus sp., Trichodorus sp., Longidorus sp., Aphelenchoides sp., Xiphinema sp. The compounds of the formula I may be used as pure active substance or together with suitable carriers and- /or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances con- (DITHIA- ventionally used in formulation technique such, for example, as solvents dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions, sprays, to solutions, or suspensions in the conventional formulation which is commonly em ployed in application terminology. Mention may also be made of cattle dips and spray races. in which aqueous preparations are used.

The agents according to the invention are manufactured in known manner by intimately mixing and/or grinding active substances of the formula l with the suitable carriers, optionally with the addition ofdispersants or solvents which are inert towards the active substances. The active substances may be available and can be used in the following forms:

Solid forms Dusts, tracking agents, granules, coated granules, im-

pregnated granules and homogeneous granules.

Liquid forms:

a. active substance concentrates dispersible in Water:

wettable powders, pastes, emulsions;

b. solutions.

To manufacture solid forms (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances can either be used alone or in admixture with one another.

Granules can be very easily manufactured by dissolving an active substance of the formula I in an organic solvent and applying the resulting solution to a granulated material, for example attapulgite, SiO granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the active substances of the formula I with polymerisable compounds (urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substances and in the process of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favourable predeterminable adsorption/desorption ratio, with the active substances, for example in the form of their solutions (in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300 g/litre to 600 g/litre can also be manufactured with the aid of atomisers. The dusting can be carried out from aircraft over extensive areas of cultures of useful plants.

It is also possible to obtain granules by compacting the carrier with the active substance and carriers and subsequently comminuting the product.

To these mixtures can also be added additives which stabilize the active substance and/or non-ionic, anionic and cationic surface active substances, which for example improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following: olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of mono-alkyl and dialkyl phenols having to ethylene oxide radicals per moecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulfonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e., wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substance and anti-foam agents and, optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitableapparatus until homogeneity is attained. Carriers are, for example, those mentioned for the solid forms of application. In some cases it is advantageous to use mixtures of different carriers. As dispersing agents there can be used, for example, condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulfonic acid, in addition, alkylaryl sulfonates, alkali and alkaline earth metal salts of dibutyl naphthalene sulfonic acid, fatty alcohol sulfates such as salts of sulfated hexadecanols, heptadecanols, octadecanols, and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salt ofoleoyl methyl tauride, ditertiary acetylene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are mixed, ground, sieved and strained with the additives mentioned above that, in wettable powder, the solid particle size of from 0.02 to 0.04 and in pasts, of 0.03 is not exceeded. To produce emulsifiable concentrates and pastes, dispersing agents such as those cited above, organic solvents and water are used. Examples of suitable solvents are the following: alcohols, benzene, xylenes, toluene, dimethyl sulfoxide, and mineral oil fractions boiling between 120 and 350 C. The solvents must be not phytotoxic, inert to the active substances.

Furthermore, the agents according to the invention can be applied in the form of solutions. For this purpose the active substance of several active substances 6 of the general formula 1 are dissolved in suitable organic solvents, mixtures of solvents or in water. A11- phatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, and mineral oils alone or mixed with each other, can be used as organic solvents.

The content of active substance in the above described agents is between 0.l% to in which connection it should be mentioned that in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99.5% or even pure active substance.

The active substances of the formula 1 can, for example, be formulated as follows:

Dusts The following substances are used to manufacture (a) a 5% and (b) a 2% dust:

a. 5 parts of active substance 95 parts of talcum b. 2 parts of active substance 1 part of highly disperse silica 97 parts of talcum.

The active substances are mixed with the carriers and ground. Granules The following substances are used to produce 5% granules:

5 pars of active substance 0.25 parts of epichlorohydrin 0.25 parts of cetyl polyglycol ether 3.50 parts of polyethylene glycol 91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polglycol ether are then added. The thus obtained solution is sprayed on to kaolin, and the acetone subsequently evaporated in vacuo.

Wettable powder:

The following constituents are used for the preparation of (a) a 40%, (b) and (c) a 25%, and (d) a 10% wettable powder:

a. 40 parts of active substance 5 parts of sodium lignin sulphonate 1 part of sodium dibutyl-naphthalene sulphonate 54 parts of silica acid.

b. 25 parts of active substance 4.5 parts of calcium lignin sulphonate 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1)

1.5 parts of sodium dibutyl naphthalene sulphate 19.5 parts of silica acid 19.5 parts of Champagne chalk 28.1 parts of kaolin.

c. 25 parts of active substance 2.5 parts of isooctylphenoxy-polyoxyethyleneethanol 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1)

8.3 parts of sodium aluminium silicate 16.5 parts of kieselgur 46 parts of kaolin.

d. 10 parts of active substance 5 parts of naphthalenesulphonic acid/formuldehyde condensate 82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. Wettable powder are obtained which can be diluted with water to give suspensions of any desired concentration.

Emulsifiable concentrates:

The following substances are used to produce (a) a 10% and (b) a emulsifiable concentrate:

a. 10 parts of active substance 3.4 parts of epoxidised vegetable oil 13.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt parts of dimethylformamide 43.2 parts of xylene.

b. 25 parts of active substance 2.5 parts of epoxidised vegetable oil 10 parts of an alkylarylsulphonate/fatty alcoholpolyglycol ether mixture 5 parts of dimethylformamide 57-5 parts of xylene.

From these concentrates it is possible to produce, by dilution with water, emulsion of any desired concentration.

Spray:

The following constituents are used to prepare a 5% spray:

5 parts of active substance 1 part'of epichlorohydrin 94 parts of benzine (boiling limits l60190 C).

The following examples will serve to illustrate the preparations of compounds according to the invention and their properties:

EXAMPLE 1 0,0-diethyl-O-[1-(2-nitrophenyl)-l,2,4-triazolyl-(3)]- thiophosphate.

a). 19.6 g l-(2-nitrophenyl)-semicarbazide and 14.8 g orthoformic acid ester were heated together with 40ml glycol monomethyl ether, whereon a clear yellow solution was obtained. The ethanol forming at an internal temperature of 120C was continuously distilled off. After 4 /2 hours the mixture was allowed to cool and treated with 200 ml ether. The compound of the formula was obtained, with a decomposition point of 276278C.

b. 40 g l-(2-nitrophenyl)-3-hydroxy-l,2,4-triazole and 23.6 g potash were heated under reflux for 1 hour together with a spatula point of copperbronze in 400 ml methyl ethyl ketone. Then 32.3 g. 0,0-diethy1-thiophosphoric acid chloride were dropped dropwise at 50C. After 3 hours heating under reflux, the solvent was evaporated in vacuo. The residue was taken up in either and washed successively with water, 0.5N HCl, saturated bicarbonate solution and brine. After drying over sodium sulphate the ether was evaporated in vacuo to leave the crude product. By filtration through 800 g silica gel using methylene chloride as solvent, the compound of the formula was obtained with a melting point of 6973C.

The following compounds were also made in analogous fashion:

R1-NN s om 1 ll 11/ on (()-I N Yin in m R3 Y 02m 0211.; o no =1,533s C1I2- pm Can; 02115 0 nD =1,.-' 310 01[- Q c2115 c2115 0 1I.D?0=1,5625

(1m (1211;. 0111;. o Snip.:5355 (1.

21T CglIr, C9115 t.) Smp.:59640.

0:1.{5 01115 O S1111).:0095C. OsN- R1 R: R3

0211:, 02115 0 CQU50 C2115 C211,; CIIJiS- l cm cm 0 (3H3 C2115 C3111 S -CII EXAMPLEZ Action against ticks A. Rhipicephalus bursa 5 Adult ticks or 50 tick larvae were counted into a glass tube and immersed for l to 2 minutes in 2 ml of an aquoeus emulsion from an emulsion series each containing 100, 10, 1 and 0.1 ppm of test substance. The tube was then sealed with a standardised cotton wool plug and placed on its head, so that the cotton wool was able to absorb the active substance emulsion.

EXAMPLE 3 Acaricidal action Phaseolus vulgaris (dwarf beans) have an infested piece of leaf from a mass culture of tetranychus urticae placed on them 12 hours before the test for the acaricidal action. The mobile stages which have migrated are sprayed with the emulsified test preparations from a chromatography atomiser so that the spray broth does not run off. The number ofliving and dead larvae, adults and eggs are evaluated ater 2 to 7 days under a stereoscopic microscope and the result expressed in percentages. During the interim, the treated plants are kept in greenhouse compartments at 25C.

The compounds according to Example 1 are active in the above test against eggs, larvae and adults of Tetranychus urticae.

EXAMPLE 4 A. Insecticidal ingest poison action Tobacco and potato plants are sprayed with a 0.05% aqueous emulsion (obtained from a emulsifiable concentrate).

After the coating has dried, Egyptian cotton leaf worms (Spodoptera literalis) are settled on the tobacco plants and Colarado potato beetle larvae (Leptinotarsa decemlineata) on the potato plants. The test is carried out at 24 C and 60% relative humidity. In the above test the compounds according to Example 1 displayed ingest poison action against Spodoprera litoralis and Leptinotarsa decemlincata.

B. Systemic insecticidal action To determine the systemic action, rooted bean plants (Vicia fabae) are put into a 0.01% aqueous active substance solution (obtained from a 10% emulsifiable concentrate). After 24 hours, aphids (Aphis fabae) are placed on the parts of the plant above the soil. The aphids are protected from contact and gas action by means ofa special device. The test is carried out at 24c and 70% relative humidity. In the above test the compounds according to Example I displayed a systemic action against Aphis fabae. i

EXAMPLE 5 Action against soil nematodes To test the action against soil nematodes, the active substance (in the concentration indicated in each case is applied to and intimately mixed with soil infected with root gall nematodes (Meloidgyne Avenaria). Immediately afterwards, tomato cuttings are planted in the thus prepared soil in a series of tests and after a waiting time of 8 days tomato seeds are sown in another test series.

In order to assess the ncmatocidal action, the galls present on the roots are counted 28 days after planting 18 and sowing respectively. The compounds according to Example I display good action aainst Meloidgyne Arenaria in this test.

What we claim is: 1. A compound of the formula wherein R represents a phenyl group (a) substituted by one or two bromine or iodine atoms, the same or different lower alkyl, lower alkoxy, lower alkylthio, lower alkyl-SO, lower alkyl-SO or O N groups or (b) substituted by one chlorine atom and one bromine or iodine atom, a lower alkyl, lower alkoxy, lower alkylthio, lower alkyl-SO, lower alkyl-SO or O N group or R. represents an unsubstituted or halogenated, lower alkylated or lower alkoxylated phenyl-lower alkyl or diphenylmethyl group, R and R each represent lower alkyl and X and Y are each oxygen or sulphur.

2. A compound according to claim 1 wherein R is 2-methyl-4-chlorophenyl, 2-nitrophenyl, 3- nitrophenyl, 4-nitrophenyl, 4-ethoxyphenyl, 4-methylmercaptophenyl, 4-bromophenyl, benzyl,

R and R are each methyl, ethyl or n-propyl, X is sulphur and Y is oxygen or sulphur.

3. The compound according to claim 2 4. The compound according to claim 2 5. The compound according to claim 2 6. The compound according to claim 2 7. The compound according to claim 2 9. The compound according to claim 2 8. The compound according to clai 2 10. The compound according to claim 2 

2. A compound according to claim 1 wherein R1 is 2-methyl-4-chlorophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 4-ethoxyphenyl, 4-methylmercaptophenyl, 4-bromophenyl, benzyl,
 3. The compound accordiNg to claim 2
 4. The compound according to claim 2
 5. The compound according to claim 2
 6. The compound according to claim 2
 7. The compound according to claim 2
 8. The compound according to claim 2
 9. The compound according to claim 2
 10. The compound according to claim 2 